Substituted aromatic aliphatic ether chlorides and process



Patented Feb. 17, 1942 SUBSTITUTED AROMATIC ALIPHATIC ETHER CHLORIDESAND PROCESS Herman A. Bruson, Philadelphia, Pa., assignor to Riihm &Haas Company, Philadelphia, Pa.

No Drawing. Original application March 29,

1938, Serial No. 198,697. Divided and this application July 5, 1940,Serial No. 344,111

19,, Claims.

This invention relates to a process for preparing complex arylpolyalkylene ether chlorides and aryloxy alkyl chlorides in which thearyl radical also carries another substituent. It relates further to aprocess whereby an aryl polyalkylene ether chloride or an aryloxy alkylchloride is condensed with a compound having an alcoholic hydroxylgroup, an olefine double bond or both in its molecule, in the presenceof a surface-active siliceous clay as a catalyst. It also relates tocertain new compounds which may be produced by this process.

The present application is a division of United States applicationSerial No. 198,697, filed March r 29, 1938 which on July 15,1941,,is'sued as United States Patent No. 2,249,111.

It is known that unsaturated ccmpcunds containing olefinic linkages, oralcohols, can be condensed with the aryl polyalkylene halides by 7 meansof catalysts of the Friedel-Crafts type as is described in theco-pending application of Bruson and Eastes, Serial No. 140,453, filedMay 3, 1937 which on July 30, 1940, issued as United.

States Patent No. 2,209,911. It is also known that compounds of similartype have been prepared by heating the substituted phenol with a,

of anhydrous zinc chloride or concentrated sulfuricacid.

or rearrange ethers and one would, therefore, expect complete break-downof aryloxy alkylene halides. r V

The clays which, are most effective for the purpose of the presentinvention are primarily aluminum hydrosilicates which may containcombined magnesium, calcium, iron, titanium .or other oxides. Many ofthese have a high absorptive capacity for the coloring matter in mineraloils and areknown, therefore, as bleaching clays. Fullers earth andbentonite belong to this class and are suitable forthe purposes of thepresent invention. Before use they are preferably washed with acid anddried at a temperature not over 150' C. In addition tothese, there aremany clays marketed under registered trade marks which arealso verysuitable. These may be purchased on the open market under the namesTonsil, Attapulgus, Floridin, Terrana or Frankonite. These clays are ofparticular value as catalysts for the herein described reactions whenone of the ingredients is a sensitive olefine or alcohol which isoftendecomposed'or polymerized by Friedel-Crafts type 'catalysts. 1

. The aryl polyalkylene ether chlorides and the aryloxy' alkyl chlorideswhich may be used in the process have the general formula pounds havealso been brought about by means p v R (OA) n01 in which R" is an arylnucleus such as benzene,

' naphthalene, phenanthreneyanthracene etc. and

These processes all have certain disadvantages which it is desirable toovercome. When working with acidic condensing agents, it is necessary toprovide acid-proof apparatus and this is particularly true in the caseof the Friedel-Crafts type of catalyst. Zinc chloride destroys the arylpolyalkylene ether chloride when the temperature is raised to the pointat which reaction takes place and sulfuric acid tends to polymerize manyolefine compounds and to dehydrate many alcohols, particularly thosehaving asecondary or tertiary hydroxyl group. i

It has now been found that condensations of this type can be broughtabout in .a simple and efficient manner'by heating the reactants in thepresence of certain clays which act as catalysts to cause theelimination of water in case one of the reactants is an alcohol or tocause the aryloxy alkylene chloride to combine with an unsaturatedcompound containing an olefine linkage. This reaction was entirelyunexpected since siliceous clays at high temperatures ordinarilydecompose which may contain other substituents which are inert in theprocess such as halogen atoms, hydroxy, alkoxy, aryloxy, hydrocarbon oracyl groups provided, of course, that the nucleus has at least onehydrogen atom available for reaction with the hydroxyl or ,olefiniccompound, A represents'an alkylene group containing at least two carbonatoms which may be a straight or branched chain, or a polyalkylene etherradical in which the alkylene groups contain at least two carbonatomsand n is an integer less than 8.

Typical ethers whichmay be used are those of the following formulas: I

ROCH2CH2C1 -R-OC4HsC1 R O(CH2) ioCl RO---CHzCH2----OCH2CH2C1 R' O--CH2CH2-O CH CH2O-CH2CH2C1 R' -(O--CH2CH2) 7C1 R 'O-CH2CH(CH3) -O-CH(CH3) CHzCl R'-OC5H10--OC5H10Cl and higher homologues. B. may be anyaryl thracyl, etc. and these groups may have other substituents aspointed out above.

These complex ether chlorides will condense with compounds having analcoholic hydroxyl group or an olefinic double bond when a mixture ofsuch substances is heated to temperatures above 150 0., preferably 180to 210 C., in the presence of a surface-active siliceous clay, theradical of the olefine or alcohol uniting with the aryl nucleus of thecomplex ether chloride.

The reaction is applicable to compounds having an alcoholic hydroxylgroup or an olefine double bond and which in addition may have othercharacteristic groups such as carboxylic, aromatic, arylaliphatic orcycloaliphatic groups.

The compounds containing olefinic double bonds which condense readilywith the complex aryl ether chlorides may be hydrocarbons, unsaturatedacids or their esters, unsaturated acids containing a hydroxyl group oran aromatic nucleus or a hydroaromatic substituent and the esters ofsuch acids. Saturated acids containing a hydroxyl group or the esters ofsuch acids may also be used. Typical of these compounds are thefollowing:

Olefines.--Butylene, isobutylene, diisobutylene, nonenes, dodecylenes(from the polymerization of propylene), diamylene, laurene, cetene,octylene-2, oleyl chloride, octahydronaphtlialene, olefines from crackedpetroleum, and other compounds of this nature.

Unsaturated acz'da-Oleic, undecylenic, linolic, linoleic,e1aeostearic,'ricinoleic and other unsaturated acids derived fromdrying, semidrying or nondrying oils, and their lower and higherhomologues.

Alcohols.-Aliphatic, arylaliphatic or hydroarylaliphatic branched orstraight chain, primary, secondary or tertiary alcohols such as amyl,hexyl, octyl, decyl, undecyl, dodecyl, myristyl, cetyl, oleyl,octadecyl, ceryl, myricyl and mixed aliphatic alcohols obtained from thehydrogenation of fats, or of carbon monoxide, octanol-Z, montanicalcohol, benzyl alcohol, phenylethyl alcohol, methyl phenyl carbinol,decahydronaphthol, cholesterol, etc.

Hydroxy acids.---hydroxystearic, ricinoleic, 9,10-dihydroxy stearic,ll-hydroxy undecylic, phenyl hydroxy stearic, cyclohexylhydroxy stearicand the esters of these acids.

The condensation is carried out in general by heating a mixture of thecomplex ether chloride and the alcohol or unsaturated compound in thepresence of the surface-active clay to temperatures above 150 0.,preferably 180 to 210 C. at ordinary pressure or in an autoclave,depending on the volatility of the reactants or product. When a compoundcontaining an alcoholic hydroxyl group is one of the reactants, water isevolved and this should preferably be removed from the reaction mixtureas fast as it is formed.

. This can be done by heating the reaction mixture under a refluxcondenser equipped with a water trap. The elimination of water may bebrought about by carryingout the reaction in the presence of a solventwhich does not take part in the reaction and which boils between about150 and 250C. The saturated cycloaliphatic hydrocarbons, such asdecaline, and saturated petroleum hydrocarbons having the proper boilingrange are suitable for the purpose. The amount of clay used is usually10% to 20% by weight calculated on the combined weight oi the reactants.More or less may be used but the above amount gives satisfactoryresults. After the condensation is complete, the clay is filtered offand the product purified by fractional distillation, preferably underreduced pressure.

The following examples will serve to illustrate the invention which,however, is not limited to the exact reactants, clays, temperature andother conditions of operation shown as it may be otherwise practicedwithin the scope of the appended claims.

EXAMPLE 1 fl-Iso-undecylphenomy-p'-chlor0diethyl ether A mixtureconsisting of 103 g. of 5-ethylnonanol-2, g. of,B-phenoxy-p-chlorodiethyl ether and 15 g. of Tonsil AS (registeredtrademark) clay was placed in a vessel equipped with an efiicientstirrer, a thermometer, and a reflux condenser attached to a water trap.The mixture was stirred vigorously and heated gradually during theperiod of an hour to 180 C., during which time about 11 cc. of Waterformed, which distilled over and was collected in the water trap. Thetemperature was then maintained at 175 to 185 C. for five hours withcontinuous agitation. The reaction product was filtered while hot, bymeans of suction, and the clear, almost colorless filtrate fractionallydistilled under re duced pressure. The product, boiling above C./0.5-1mm., was refractionated and yielded 61 g. of an iso-undecylphenoxyethoxyethyl chloride [3-(5'60. octyZ-Z-naphthozy)-o'-chlorodiethyl ether Amixture consisting of 45 g. of octanol-2, 75 g. ofp-(Z-naphthoxy)-p'-chlorodiethyl ether, and 12 g. of Tonsil clay wasstirred and heated underreflux during one and one-half hours to C., andat 175 to C. for three additional hours, during which time 7 cc. ofwater collected in the water trap attached to the reflux condenser. Thefiltered reaction product, after fractionation in vacuo, yielded thecompound Ca nas a pale yellow oil boiling at 210-220 C./1 mm.

The octanol-Z can be replaced by hexanol-Z, heptanol-2, or nonanol-2 toyield the homologous sec. hexyl-, sec. heptyl-, and sec.nonyl-naphthoxyethoxy ethyl chlorides, which are highboiling yellowoils.

EXAMPLE 3 Grams Ethyl-ricinoleate (1/3 mol) (B. P. 200-205 C./1 mm.) 108c-Phenoxy-p'-chlorodiethyl ether (1 mol) 200 Tonsil clay 30 The abovemixture was heated, while stirring for one-half hour, to 180 0., under areflux condenser attached to a water trap, during which time 6 00. ofwater collected in the trap. The temperature was then maintained at 180C. for four hours, during which time 2 co. more water came over. Theproduct was filtered'hotand the excess ,c-phenoxy-c-ch1or0diethyletherrecovered by fractionation in vacuo. In this manner, 135 g. ofc-phenoxy-p-chlorodiethyl ether b iling at 113-120 C./1 mm. wasrecovered. The residual oil was heated under 1 mm. pressure to 220 C.,'but no unchanged ethyl ricinoleate 'the free acid obtained by acidifyingthe solution of the alkali metal salt. From this acid other esters andsalts of organic or inorganic bases can be preparedin any conventionalmanner.

EXAMPLE 4 A mixture consisting of 91 g. of oleic acid, 134 g. ofB-phenoxy-{i'-chlorodiethyl ether, and 23 g. of Tonsil clay was heatedwith stirring for four hours at 185 to 200 C. under a reflux condenser.The filtered product was then distilled in high vacuo to remove allunchanged materials until the vapor temperature reached 200 C./ 0.5 mm.The residue was a reddish oil weighing 110 g. and contained 6.5%chlorine. l

The resulting chloroethoxyethoxy phenyl stearic acid may be converted toesters or salts of organic or inorganic bases as desired.

EXAMPLE 5 A mixture consisting of 61 g. of methylphenyl carbinol, 150 g.of B-phenoxy-B'-chlorodiethyl ether, and g. of Tonsil clay was stirredand heated for four hours at 180 to 190 C. under reflux attached to awater trap. The filtered A mixture consisting of 100 g. of c-phenoxy;8-chlorodiethyl ether,'54 g. of benzyl alcohol and 7.7 'g. of Tonsilclay was stirred and heated for three hours at 170 to 180", C. underreflux attached to a water trap. The product was filtered and thefiltrate fractionated in vacuo.

Benzylphenoxyethoxyethyl chloride came over at 200-220 .C. /3 mm.

EXAMPLE 7 A mixture, consisting of 80 g. of c-phenoxyfi 'chlorodiethylether, 10. g. of Tonsil clay, and 49 g. of higher alcohols from themethanol synthesis, boiling at 190 to 210 C. and consisting of mixedprimary and secondary branched chain monohydric alcohols, containingfrom about 9 to 12 carbon atoms resulting from the catalytic re- 3duction of carbon monoxidewith hydrogen, was heated for four hours, withstirringunderreflux attached to awater trap. The filtered product, uponfractionation in vacuo, yielded the mixed C9-C12 alkylphenoxyethoxyethylchlorides as a pale yellow oil boiling at 180-220 C./ 2 mm.

EXAMPLE 8 A mixture consisting of 180 g. of fi-phenoxyc.-chlorodiethylether, 117 g. of octanoL-2, and 20 g. of Tonsil clay was heated withstirring for four hours at 160175 C. under reflux attached to a watertrap. The sec. octyl-phenoxy -ethoxyethyl chloride was obtained in 60%yield as a pale yellow oil, B. P. 175-185 C./3 mm.

, V EXAMPLE 9 r A mixture, consisting of 109 g. of ethyl-10 hydroxystearate, 122 g. of p-phenoxy-;3'-chlorodiethyl ether and 23 g. ofTonsil clay, was stirred and heated for four hours at 180 to 185 C.under a reflux condenser attached to a water trap. The product wasfiltered and the filtrate distilled in vacuo at 1-2 mm. until the vaportemperature reached 210 C. The still residue, weighing 127 g., wasclarified with bleaching clay. It contained 6% chlorine by analysis.Theoretical chlorine is 6.95% for This ester may be. saponified withalkali and the free acid obtained byacidifying the solution of thealkali metal salt.v From this acid other esters and salts of organic orinorganic base can be prepared in any conventional manner.

EXAMPLE 10,

A mixture,consisting of 56 g. of {3-phenoxyethyl chloride, 66.5 g. ofdodecyl alcohol. and 15 g. of acid-washed Tonsil bleaching earth, wasrefluxed three and one-quarter hours at 167 to 195 C., during which time2.5 cc. of waterwas removed in a separator and the remaining .distillatereturned'to the reaction mixture. Heating was continued for anadditional sixteen hours at 195 to 181 C. The reaction mixture wasdiluted with toluene-filtered from the clay, and distilled in vacuo. Thefi-chloro ethyl ether of dodecyl phenol was obtained'as a pale yellowoil, 97.5% pure, B. P. 180200 C./1 mm.

EXAMPLE 11 A mixture consisting of 112 g. of n-butyl oleate (B. P.178188 C./1 mm.), 100 g. of fl-phenoxypV-chlorodiethyl ether and 20 g.of Tonsil clay was heated under reflux, with rapid stirring, fo r Iabout six hours at 186 to 195 C. The filtered oil was then distilled invacuo until the vapor temperature reached 210 C. at 1 mm. pressure. Theresidue, weighing 125 g., was a dark oil containing 5.5% chlorine andhaving an acid number 88.4, indicating substantial addition of thephenyl nucleus to the double bond had occurred,

' together with somehydrolysis' of the ester group;

I :EXAMPLE 12 I A mixture, consisting of 76 g. of decahy'dro-.B-naphthol, 100 'g. of B-phenoxy-fi-chlorodiin which A, n and R havethe meanings given above, Y is an aliphatic hydrocarbon chain which mayalso have a double bond or an aromatic or hydroaromatic substituent, andM is hydrogen,

a hydrocarbon radical or a basic organic or inorganic salt-forming groupor a metal.

All of the complex aryloxy alkyl or aryl polyalkylene ether chloridesdescribed herein are useful intermediates for preparing water-solublecapillary-active compounds.- For example, the aromatic ring may besulfonated' to yield watersoluble sulfonic acids which along with theirwater-soluble salts of organic or inorganic bases are good wetting,cleansing, dispersing and emulsifying agents. The terminal chlorine atommay be replaced by an --SOsNa group as is described in my co-pendingapplication Serial No. 187,158 filed January 27, 1938, which on February28, 1939, issued as United States Patent No. 2,148,432, by heating thecomplex ether chloride with aqueous sodium sulfite. The free sulfonicacid can be prepared from the sodium salt and can be converted intoother salts of organic or inorganic bases.

The complex aryl ether halides also react with ammonia, primary,secondary or tertiary amines which may contain sulfonie or carboxylicacid groups whereby the RR"-\(OA)n group is attached to the nitrogenatom and forms amines or quaternary ammonium salts.

Thio ethers may be prepared by heating the complex ether with sodiumsulfide and the mercaptans by heating with sodium hydrosulfide. Causticsoda at high temperatures will replace the chlorine. atom with ahydroxyl group. By heating the complex ether chlorides with an alcoho].X-OH and an alkali, the chlorine atom is removed and the etherRR'(OA)nOX is formed.

All of the derivatives and further reaction products of the complexether chlorides are also very useful for preparing capillary-activesubstances which are good wetting, dispersing, cleansing, andemulsifying agents.

In the foregoing description the complex ether chlorides have been usedas illustrations. It is, of course, possible to carry out the samereactions with the corresponding bromides and iodides.

I claim:

1. The process which comprises reacting by heating in the presence of asurface-active siliceous clay an ether chloride of the formula in whichR. is an aryl nucleus, A is a group se-- lected from the classconsisting of alkylene radicals having a chain of at least two carbonatoms and polyalkylene ether radicals having at least two carbon atomsin each alkylene group, and n is an integer less than 8 and a member ofthe group consisting of unsaturated and hydroxy-' substituted highercarboxylic acids and esters selected from the aliphatic, arylaliphatic,and hydroarylaliphatic series.

2. The process which comprises reacting by heating in the presence of asurface-active siliceous clay an ether chloride of the formula in whichR is an aryl nucleus, A is a group selected from the class consisting ofalkylene radi cals having a chain of at least two carbon atoms andpolyalkylene ether radicals having at least two carbon atoms in eachalkylene group, and n is an integer less than 8 and a member of thegroup consisting of unsaturated and hydroxysubstituted higher carboxylicacids and esters of the aliphatic series.

3. The process which comprises reacting by heating in the presence of asurface-active siliceous clay an etherchloride of the formula in which Ris an aryl nucleus, A is a group selected from the class consisting ofalkylene radicals having a chain of at least two carbon atoms andpolyalkylene ether radicals having at least two carbon atoms in eachalkylene group, and n is an integer less than 8 and an unsaturatedhigher carboxylic acid selected from the aliphatic, arylaliphatic andhydroarylaliphatic series.

4. The process which comprises reacting by heating in the presence of asurface-active siliceous clay an ether chloride of the formula in whichR is an aryl nucleus, A is a group selected from the class consisting ofalkylene radicals having a chain of at'least two carbon atoms andpolyalkylcne ether radicals having at least two carbon atoms in eachalkylene group, and n is an integer less than 8 and an unsaturated fattyacid.

5, The process which comprises reacting by heating in the presence of asurface-active siliceous clay an ether chloride of the formula in whichR is an aryl nucleus, A is a group selected from the class consisting ofalkylene radicals having a chain of at least two carbon atoms andpolyalkylene ether radicals having at least two carbon atoms in eachalkylene group, and n is an integer less than 8 and a hydroxy aliphatichigher carboxylic acid.

6. The process which comprises reacting by heating in the presence of asurface-active siliceous clay an ether chloride of the formula in whichR is an aryl nucleus, A is a group selected from the class consisting ofalkylene radicals having a chain of at least two carbon atoms andpolyalkylene ether radicals having at least two carbon atoms in eachalkylene group, and n is an integer less than 8 and an ester of anunsaturated higher carboxylic acid selected from the aliphatic,arylaliphatic, and hydroarylaliphatic series.

7. The process which comprises reacting by heating in the presence of asurface-active siliceous clay an ether chloride of the formula in whichR is an aryl nucleus, A is a group selected from the class consisting ofalkylene radicals having a chain of at least two carbon atoms andpolyalkylene ether radicals having at least two carbon atoms in eachalkylene group,

and n is an integer less than 8 and an ester of a hydroxyl-containingfatty acid. 9

8. The process for condensing p-chloroethoxyethoxy benzene andricinoleic acid Which comprises heating said reactants to a temperatureof from about 180 C. to about 216 C. in the presence of a surface-activesiliceous clay.

9. The p ocess for condensing fi-chloroethoxyethoxy benzene and oleicacid which comprises heating said reactants to a temperature of fromabout 180 C. to about 210 C. in the presence 0 a surface-activesiliceous clay.

10. The process for condensing B-cholorethoxyethoxy benzene and ethylIO-hydroxy stearate which comprises heating a mixture of said re actantsat a temperature between about 180 C. and about 210 C. in' the presenceof a surfacen is an integer less than 8, Y is a member of the classconsisting of aliphatic, arylaliphatic, and hydroarylaliphatic groups.

12; Compounds having in their acidic form the I in which R is an arylnucleus, A is a group selected from the class consisting of alkyleneradi- 1 cals having a chain of at least two carbon atoms andpolyalkylene ether radicals having at least two carbon atoms in eachalkylene group, n is an integer less than 8, Y is an aliphatichydrocarbon group.

l3, Compounds having in their acidic form the formula 'in which R is anaryl nucleus, A is a group selected from the class consisting ofalkylene radicals having a chain of at least two carbon atoms andpoiyalkylene ether radicals having at least two carbon atoms in eachalkylene group, n is an integer less than'8, Y is the hydrocarbon chainof ricinoleic acid.

l4. Compounds having in their acidic form the formula inwhich R is anaryl nucleus, A is a group selected from the class consisting ofalkylene radiclay. p r 16. The compound obtained by condensing calshaving a chain of at least two carbon atoms and polyalkylene etherradicals having at least two carbon atoms in each alkylene group, n isan integer less than 8, Y is the hydrocarbon chain of stearic acid. 7

15. The compound obtained by condensing ricinoleic acid with,B-chloroethoxyethoxy benzene in the presence of a surface-activesiliceous oleic acid with p-chloroethoxyethoxy benzene in the presenceof a surface-active siliceous clay.

1'7. The compound obtained by condensing an ester of an aliphatichydroxyl-containing car boxylic acid with fi-chloroethoxyethoxy benzenein the presence of a surface-active siliceous clay. A

18. The compound obtained by condensing an ester of hydroxystearic acidwith fl-chloroethoxyethoxy benzene in the presence of a surface-activesiliceous clay.

19; The compound obtained by condensing ethyl IO-hydroxystearate withp-chloroethoxyethoxybenzene in the presence of a surfaceactive siliceousclay.

HERMAN A. BRUSON.

